KR20190038804A - Photocurable clear ink composition for inkjet printing - Google Patents

Photocurable clear ink composition for inkjet printing Download PDF

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KR20190038804A
KR20190038804A KR1020197002029A KR20197002029A KR20190038804A KR 20190038804 A KR20190038804 A KR 20190038804A KR 1020197002029 A KR1020197002029 A KR 1020197002029A KR 20197002029 A KR20197002029 A KR 20197002029A KR 20190038804 A KR20190038804 A KR 20190038804A
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ink composition
clear ink
mass
inkjet printing
acrylate
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KR1020197002029A
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Korean (ko)
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오키노리 나카시마
다쿠야 묘세
다쿠야 오카모토
가즈히로 후케
료이치 닛타
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사카타 인쿠스 가부시키가이샤
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Priority to KR1020227000354A priority Critical patent/KR102463006B1/en
Publication of KR20190038804A publication Critical patent/KR20190038804A/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C—CHEMISTRY; METALLURGY
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    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
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    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
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    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/103—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds of aldehydes, e.g. phenol-formaldehyde resins
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    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
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    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium

Abstract

클리어 잉크는 열에 의한 마이크로겔화가 일어나기 쉬워 저장 안정성이 저하될 가능성이 있으며, 또한 클리어 잉크가 시간 경과에 따라 마이크로겔이 발생하면 잉크젯 토출성이 저하되는 과제가 있다. 해결방법으로서 광중합성 화합물, 광중합개시제 및 평균 입경 1~200 ㎚의 무기 필러를 조성물 중 0.05~5.0 질량% 함유하고, 가시광 투과율이 30% 이상인 광경화형 잉크젯 인쇄용 클리어 잉크 조성물을 제공한다. There is a possibility that the clear ink tends to be microgelled by heat and the storage stability may be lowered. In addition, there is a problem that when the clear ink develops microgel over time, ink jet dischargeability is lowered. The present invention provides a clear ink composition for photocurable inkjet printing comprising a photopolymerizable compound, a photopolymerization initiator, and an inorganic filler having an average particle diameter of 1 to 200 nm in an amount of 0.05 to 5.0 mass% in the composition and a visible light transmittance of 30% or more.

Description

광경화형 잉크젯 인쇄용 클리어 잉크 조성물{PHOTOCURABLE CLEAR INK COMPOSITION FOR INKJET PRINTING}[0001] PHOTOCURABLE CLEAR INK COMPOSITION FOR INKJET PRINTING [0002]

본 발명은 광경화형 잉크젯 인쇄용 클리어 잉크 조성물에 관한 것이다. The present invention relates to a clear ink composition for photocurable inkjet printing.

광경화형 잉크젯 인쇄용 클리어 잉크 조성물로서 특허문헌 1에 기재되어 있는 조성물은 공지이다. 이러한 조성물은 클리어 잉크 조성물 중에 착색안료나 체질안료를 함유하지 않고, 경화성 성분 및 경화제 등의 첨가물만으로 이루어지는 조성물이다. 그리고, 컬러잉크에 의한 기록물 표면 위에 추가로 클리어 잉크 조성물을 인쇄함으로써, 그 기록물 표면에 매트한 느낌을 부여할 수 있다. The composition disclosed in Patent Document 1 as a clear ink composition for photocurable inkjet printing is known. Such a composition does not contain a coloring pigment or extender pigment in a clear ink composition, but is a composition comprising only additives such as a curing component and a curing agent. Further, by printing a clear ink composition on the surface of the recording material by the color ink, a matte feeling can be given to the surface of the recording material.

또한 특허문헌 2에 기재된 광경화형 잉크젯 인쇄용 클리어 잉크 조성물은 금속 분말이나 착색제를 함유하지 않고, 금속 분말을 포함하는 잉크를 인쇄하기 전에 기록 매체에 인쇄함으로써 기록 매체의 평활성을 향상시켜, 금속 분말을 포함하는 잉크에 의한 광택감이나 고급감을 우수한 것으로 할 수 있다.Also, the clear ink composition for photocurable inkjet printing described in Patent Document 2 improves the smoothness of the recording medium by printing on a recording medium before printing the ink containing the metal powder without containing the metal powder or the colorant, It is possible to obtain an excellent gloss feeling and high quality.

또한 특허문헌 3에 기재되어 있는 바와 같이, 광중합성 잉크젯 착색 잉크에 있어서 실리카를 배합함으로써 경화물의 경도를 올려 내찰과성을 향상시키는 것은 공지이며, 또한 특허문헌 4에 기재되어 있는 바와 같이, 광경화형 잉크젯 잉크에 무기계 자외선 흡수제인 산화아연, 산화세륨, 루틸형 산화티탄을 배합시켜서, 자외선에 의한 변퇴색을 효과적으로 방지할 수 있는 것도 공지이다. Further, as described in Patent Document 3, it is known that the hardness of a cured product is increased by blending silica in a photopolymerizable inkjet colored ink to improve abrasion resistance and, as described in Patent Document 4, It is also known that zinc oxide, cerium oxide, and rutile-type titanium oxide, which are inorganic ultraviolet absorbers, are blended in an inkjet ink to effectively prevent discoloration by ultraviolet rays.

일본국 특허공개 제2015-057330호 공보Japanese Patent Application Laid-Open No. 2015-057330 일본국 특허공개 제2014-172986호 공보Japanese Patent Application Laid-Open No. 2014-172986 일본국 특허공개 제2015-081294호 공보Japanese Patent Application Laid-Open No. 2015-081294 일본국 특허공개 제2011-219648호 공보Japanese Patent Application Laid-Open No. 2011-219648

LED 등을 광원으로 하는 빛에 의해 경화되는 광경화형 잉크젯 인쇄용 클리어 잉크 조성물은 아크릴레이트를 라디칼 중합시킴으로써 경화 도막을 형성하기 때문에 높은 반응성이 요구되고 있다. 한편, 높은 반응성을 가지면 열에 의한 반응성도 높아지는 경향이 있다. 이때에는 열에 대한 안정성이 저하되어 잉크의 저장 안정성이 악화되게 된다. 이 때문에 빛에 대한 반응성을 높게 하면서 열에 대한 반응성을 낮게 하는 것이 필요해진다. A clear ink composition for photocurable inkjet printing which is cured by light using an LED or the like as a light source is required to have high reactivity because it forms a cured coating film by radical polymerization of acrylate. On the other hand, if the reactivity is high, the reactivity due to heat tends to be high. At this time, the stability against heat is deteriorated and the storage stability of the ink deteriorates. For this reason, it is necessary to lower reactivity to heat while increasing reactivity to light.

특히 클리어 잉크는 열에 의한 마이크로겔화가 일어나기 쉽고, 저장 안정성이 저하될 가능성이 있으며, 또한 클리어 잉크가 시간의 경과에 따라 마이크로겔이 발생하면 잉크젯 토출성이 저하될 가능성이 있다. In particular, clear ink tends to cause micro gelling due to heat, and there is a possibility that the storage stability is lowered. In addition, if a clear ink develops a microgel over time, there is a possibility that ink jet dischargeability is lowered.

본 발명자들은 광경화형 잉크젯 인쇄용 클리어 잉크 조성물로서, As a clear ink composition for photocurable inkjet printing,

1. 광중합성 화합물, 광중합개시제 및 평균 입경 1~200 ㎚의 무기 필러를 조성물 중 0.05~5.0 질량% 함유하고, 가시광 투과율이 30% 이상인 광경화형 잉크젯 인쇄용 클리어 잉크 조성물, 1. A clear ink composition for photocurable inkjet printing comprising a photopolymerizable compound, a photopolymerization initiator and 0.05 to 5.0 mass% of an inorganic filler having an average particle diameter of 1 to 200 nm in the composition and having a visible light transmittance of 30%

2. 무기 필러가 실리카 및/또는 산화알루미늄인 1에 기재된 광경화형 잉크젯 인쇄용 클리어 잉크 조성물, 2. A clear ink composition for photocurable inkjet printing according to 1 wherein the inorganic filler is silica and / or aluminum oxide,

3. 아미노기 및/또는 산기를 갖는 안료 분산제를 함유하는 1 또는 2에 기재된 광경화형 잉크젯 인쇄용 클리어 잉크 조성물, 3. A clear ink composition for photocurable inkjet printing according to 1 or 2, which contains a pigment dispersant having an amino group and / or an acid group,

4. 광중합성 화합물로서, 광경화형 잉크젯 인쇄용 클리어 잉크 조성물 중에 아미드기를 갖는 단관능 모노머와 벤질아크릴레이트의 합계량으로 50~75 질량% 함유하는 1 내지 3 중 어느 하나에 기재된 광경화형 잉크젯 인쇄용 클리어 잉크 조성물, 4. A clear ink composition for photocurable inkjet printing as described in any one of 1 to 3, wherein the photopolymerizable compound contains 50 to 75% by mass of the total amount of a monofunctional monomer having an amide group and benzyl acrylate in a clear ink composition for photocurable inkjet printing ,

5. 아미드기를 갖는 단관능 모노머가 N-비닐카프로락탐 및/또는 아크릴로일모르폴린인 1 내지 4 중 어느 하나에 기재된 광경화형 잉크젯 인쇄용 클리어 잉크 조성물, 5. The clear ink composition for photocurable inkjet printing according to any one of 1 to 4, wherein the monofunctional monomer having an amide group is N-vinylcaprolactam and / or acryloylmorpholine,

6. 25℃의 점도가 10 mPa·s 이하인 1 내지 5 중 어느 하나에 기재된 광경화형 잉크젯 인쇄용 클리어 잉크 조성물6. The clear ink composition for photocurable inkjet printing according to any one of 1 to 5, wherein the viscosity at 25 占 폚 is 10 mPa 占 퐏 or less

을 채용함으로써 상기 과제를 해결할 수 있는 것을 발견하고, 본 발명을 해결하기에 이르렀다. The above problems can be solved, and the present invention has been accomplished.

본 발명에 의하면, 특정 조성으로 이루어지는 광경화형 잉크젯 인쇄용 클리어 잉크 조성물로 함으로써, 자외선, 특히 발광 다이오드(LED)를 광원으로 한 자외선에 의한 박막에서의 경화성이 우수함과 동시에 열에 대한 안정성을 향상시켰기 때문에, 잉크 조성물의 보존 안정성을 향상시킬 수 있었다.According to the present invention, since the clear ink composition for a photo-curable inkjet printing having a specific composition is excellent in curability in a thin film by ultraviolet rays, particularly ultraviolet rays using a light emitting diode (LED) as a light source, The storage stability of the ink composition could be improved.

아래에 본 발명의 광경화형 잉크젯 인쇄용 클리어 잉크 조성물(이하, 본 발명의 잉크 조성물이라고도 함)에 대해서 상세하게 설명한다. Hereinafter, the clear ink composition for photocurable inkjet printing of the present invention (hereinafter also referred to as the ink composition of the present invention) will be described in detail.

본 발명은 광중합성 화합물, 광중합개시제 및 안료를 함유하는 광경화형 잉크젯 인쇄용 잉크 조성물에 있어서 그 안료의 평균 입경과 함유량을 검토함으로써, 가시광 투과율이 30% 이상인 클리어 잉크 조성물로 하는 것이다. The present invention provides a clear ink composition having a visible light transmittance of 30% or more by examining the average particle size and content of the pigment in a photocurable inkjet printing composition containing a photopolymerizable compound, a photopolymerization initiator and a pigment.

＜광중합성 화합물＞ ≪ Photopolymerizable compound >

본 발명의 잉크 조성물은 광중합성 화합물로서 단관능 모노머나 다관능 모노머를 함유할 수 있다.The ink composition of the present invention may contain a monofunctional monomer or a polyfunctional monomer as a photopolymerizable compound.

(단관능 모노머) (Monofunctional monomer)

단관능 모노머로서는 메틸메타크릴레이트, 부틸메타크릴레이트, 2-에틸헥실메타크릴레이트, 메틸아크릴레이트, 부틸아크릴레이트, 2-에틸헥실아크릴레이트 등의 알킬(메타)아크릴레이트, 이소보르닐(메타)아크릴레이트, 페녹시에틸(메타)아크릴레이트, 4-t-부틸시클로헥실(메타)아크릴레이트, 디시클로펜테닐(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트 등의 지환식 단관능 모노머, 벤질메타크릴레이트 등의 아랄킬(메타)아크릴레이트, 부톡시에틸메타크릴레이트, 부톡시에틸아크릴레이트 등의 알콕시알킬(메타)아크릴레이트, 트리에틸렌글리콜모노부틸에테르, 디프로필렌글리콜모노메틸에테르 등의 폴리알킬렌글리콜모노알킬에테르의 (메타)아크릴산에스테르, 헥사에틸렌글리콜모노페닐에테르 등의 폴리알킬렌글리콜모노아릴에테르의 (메타)아크릴산에스테르, 글리세롤(메타)아크릴레이트, 2-히드록시에틸(메타)아크릴레이트 등의 광중합성 모노머, 에폭시(메타)아크릴레이트, 폴리에스테르(메타)아크릴레이트, 폴리에테르(메타)아크릴레이트 등의 광중합성 올리고머, 아크릴아미드, 메타크릴아미드, 디에틸아크릴아미드, N,N-디메틸아크릴아미드, N,N-디메틸메타크릴아미드, N,N-디에틸아크릴아미드, N,N-디에틸메타크릴아미드, N,N'-메틸렌비스아크릴아미드, N,N-디메틸아미노프로필아크릴아미드, N,N-디메틸아미노프로필메타크릴아미드, 디아세톤아크릴아미드, (메타)아크릴로일모르폴린, N-비닐카프로락탐, N-비닐피롤리돈 등의 아미드기 및/또는 아미노기를 갖는 단관능 모노머, 아미노에틸(메타)아크릴레이트, N,N-디메틸아미노에틸(메타)아크릴레이트, N,N-디메틸아미노프로필(메타)아크릴레이트 등의 아미노기를 갖는 단관능 모노머 등이 예시된다. 이들 단관능 모노머는 1종 또는 2종 이상 사용할 수 있다.Examples of the monofunctional monomer include alkyl (meth) acrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate and 2-ethylhexyl acrylate, Alicyclic monofunctional monomers such as acrylate (meth) acrylate, phenoxyethyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate and cyclohexyl (Meth) acrylate such as benzyl methacrylate, alkoxyalkyl (meth) acrylate such as butoxyethyl methacrylate and butoxyethyl acrylate, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether (Meth) acrylic acid esters of polyalkylene glycol monoalkyl ethers such as hexaethylene glycol monophenyl ether, (Meth) acrylate, polyether (meth) acrylate, polyether (meth) acrylate, polyether (meth) acrylate, Acrylamide, N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, N, N-diethylacrylamide, N, N-diethyl N, N'-methylenebisacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminopropylmethacrylamide, diacetone acrylamide, (meth) acryloylmorpholine, N - monofunctional monomers having an amide group and / or an amino group such as vinylcaprolactam and N-vinylpyrrolidone, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) Dimethylaminopropyl (meth) acrylate And monofunctional monomers having an amino group such as a carboxyl group and a carboxyl group. These monofunctional monomers may be used alone or in combination of two or more.

단관능 모노머의 함유량은 클리어 잉크 조성물 중 40 질량% 이상이 바람직하고, 50 질량% 이상인 것이 더욱 바람직하다. 또한, 단관능 모노머의 함유량은 클리어 잉크 조성물 중 90 질량% 이하가 바람직하고, 80 질량% 이하인 것이 보다 바람직하며, 더욱 바람직하게는 75 질량% 이하이다. The content of the monofunctional monomer in the clear ink composition is preferably not less than 40% by mass, more preferably not less than 50% by mass. The content of the monofunctional monomer in the clear ink composition is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less.

단관능 모노머의 함유량이 40 질량% 미만인 경우, 얻어지는 경화 도막은 밀착성이 저하될 가능성이 있다. 한편, 단관능 모노머의 함유량이 90 질량%를 초과하는 경우, 얻어지는 경화 도막은 점착성, 내찰성이 저하될 가능성이 있다. If the content of the monofunctional monomer is less than 40% by mass, the resulting cured coating film may have poor adhesion. On the other hand, when the content of the monofunctional monomer is more than 90% by mass, the resulting cured coating film may be deteriorated in tackiness and scratch resistance.

이들 단관능 모노머 중에서도, 얻어지는 경화 도막의 점착성 및 경화성을 향상시키기 위해, 조성물 중에 있어서 아미드기를 갖는 단관능 모노머와 벤질아크릴레이트의 합계량으로 50~75 질량% 함유하는 것이 바람직하다. Among these monofunctional monomers, in order to improve the tackiness and curability of the resulting cured coating film, it is preferable that the composition contains 50 to 75% by mass of the total amount of the monofunctional monomer having amide group and benzyl acrylate.

바람직한 아미드기를 갖는 단관능 모노머로서는 N-비닐카프로락탐 및/또는 아크릴로일모르폴린을 예시할 수 있다. As the monofunctional monomer having a preferable amide group, N-vinylcaprolactam and / or acryloylmorpholine can be exemplified.

＜다관능 모노머＞ <Multifunctional Monomers>

다관능 모노머로서는 분자 내에 2개의 광중합성 관능기 및 2개의 아미노기를 갖는 아크릴화 아민 화합물, 비닐옥시에톡시에틸(메타)아크릴레이트, 1,4-부탄디올디(메타)아크릴레이트, 1,6-헥산디올디(메타)아크릴레이트, 에틸렌글리콜디(메타)아크릴레이트, 디에틸렌글리콜디(메타)아크릴레이트, 트리에틸렌글리콜디(메타)아크릴레이트, 테트라에틸렌글리콜디(메타)아크릴레이트, 폴리에틸렌글리콜디(메타)아크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트, 프로필렌글리콜디(메타)아크릴레이트, 디프로필렌글리콜디(메타)아크릴레이트, 트리프로필렌글리콜디(메타)아크릴레이트, 에톡시화 1,6-헥산디올디(메타)아크릴레이트, 에톡시화 네오펜틸글리콜디(메타)아크릴레이트, 에톡시화 비스페놀 A 디(메타)아크릴레이트, 시클로헥산디메탄올디(메타)아크릴레이트, 알콕시화 헥산디올디(메타)아크릴레이트, 알콕시화 시클로헥산디메탄올디(메타)아크릴레이트, 알콕시화 디(메타)아크릴레이트, 트리시클로데칸디메탄올디(메타)아크릴레이트, 프로폭시화 네오펜틸글리콜디(메타)아크릴레이트, 알콕시화 네오펜틸글리콜디(메타)아크릴레이트, 알콕시화 지방족 디(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 트리스(2-히드록시에틸)이소시아누레이트트리(메타)아크릴레이트, 펜타에리스리톨트리(메타)아크릴레이트, 에톡시화 트리메틸올프로판트리(메타)아크릴레이트, 프로폭시화 트리메틸올프로판트리(메타)아크릴레이트, 프로폭시화 글리세릴트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 디트리메틸올프로판테트라(메타)아크릴레이트, 에톡시화 펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨펜타(메타)아크릴레이트 등이 예시된다. 이들 다관능 모노머를 1종 또는 2종 이상 사용할 수 있다. Examples of the polyfunctional monomer include an acrylated amine compound having two photopolymerizable functional groups and two amino groups in the molecule, vinyloxyethoxyethyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6- Acrylate, diethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di Acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethoxylated 1,6- (Meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, cyclohexanedimethanol di (Meth) acrylate, alkoxylated hexanediol di (meth) acrylate, alkoxylated cyclohexanedimethanol di (meth) acrylate, alkoxylated di (meth) acrylate, tricyclodecanedimethanol di Acrylate, alkoxylated neopentyl glycol di (meth) acrylate, alkoxylated aliphatic di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (2-hydroxyethyl (Meth) acrylates such as isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol Such as tall tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like. One or more of these polyfunctional monomers may be used.

다관능 모노머의 함유량은 클리어 잉크 조성물 중 15 질량% 이상이면 되고, 20 질량% 이상인 것이 바람직하다. 또한, 다관능 모노머의 함유량은 클리어 잉크 조성물 중 50 질량% 이하면 되고, 35 질량% 이하인 것이 바람직하다. 다관능 모노머의 함유량이 15 질량% 미만인 경우, 얻어지는 경화 도막은 내찰성, 점착성이 저하되기 쉽다. 한편, 다관능 모노머의 함유량이 50 질량%를 초과하는 경우, 얻어지는 경화 도막은 밀착성이 저하되기 쉽다. The content of the polyfunctional monomer in the clear ink composition should be not less than 15% by mass, preferably not less than 20% by mass. The content of the polyfunctional monomer in the clear ink composition is preferably 50% by mass or less, more preferably 35% by mass or less. When the content of the polyfunctional monomer is less than 15% by mass, the resulting cured coating film tends to have poor scratch resistance and tackiness. On the other hand, when the content of the polyfunctional monomer exceeds 50 mass%, the resulting cured coating film tends to have poor adhesion.

＜광중합개시제＞ <Photopolymerization initiator>

광중합개시제로서는 아실포스핀계 광중합개시제나 트리아진계 광중합개시제 등의 임의의 것을 채용할 수 있다. As the photopolymerization initiator, any of an acylphosphine-based photopolymerization initiator and a triazine-based photopolymerization initiator may be employed.

아실포스핀계 광중합개시제는 아실포스핀기를 포함하는 광중합개시제로, 트리아진계 광중합개시제는 트리아진 구조를 갖는 광중합개시제이다. 이들 광중합개시제는 450~300 ㎚의 파장 전역에 걸쳐 광 흡수 특성을 가져, 이들 특정 파장의 빛(UV-LED)의 조사를 받아 클리어 잉크 조성물을 중합시켜 고분자화한다. The acylphosphine-based photopolymerization initiator is a photopolymerization initiator containing an acylphosphine group, and the triazine-based photopolymerization initiator is a photopolymerization initiator having a triazine structure. These photopolymerization initiators have light absorption properties over a wavelength range of 450 to 300 nm and are polymerized by polymerizing the clear ink composition upon irradiation with light of these specific wavelengths (UV-LED).

아실포스핀계 광중합개시제로서는 2,4,6-트리메틸벤조일디페닐포스핀옥사이드, 2,6-디메톡시벤조일디페닐포스핀옥사이드, 2,6-디클로로벤조일디페닐포스핀옥사이드, 2,3,5,6-테트라메틸벤조일디페닐포스핀옥사이드, 2,6-디메틸벤조일디메틸포스핀옥사이드, 4-메틸벤조일디페닐포스핀옥사이드, 4-에틸벤조일디페닐포스핀옥사이드, 4-이소프로필벤조일디페닐포스핀옥사이드, 1-메틸시클로헥사노일벤조일디페닐포스핀옥사이드, 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드, 2,4,6-트리메틸벤조일페닐포스핀산메틸에스테르, 2,4,6-트리메틸벤조일페닐포스핀산이소프로필에스테르, 비스(2,6-디메톡시벤조일)-2,4,4-트리메틸펜틸포스핀옥사이드, 비스(2,6-디메톡시벤조일)-2,3,3-트리메틸-펜틸포스핀옥사이드 등이 예시된다. 구체적으로는, 2,4,6-트리메틸벤조일-디페닐-포스핀옥사이드로서 TPO(Lamberti사 제조), 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드로서 IRGACURE819(BASF사 제조) 등이 예시된다. As the acylphosphine-based photopolymerization initiator, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5 , 6-tetramethylbenzoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldimethylphosphine oxide, 4-methylbenzoyldiphenylphosphine oxide, 4-ethylbenzoyldiphenylphosphine oxide, 4-isopropylbenzoyldiphenyl (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2, 3-trimethylbenzoylphenylphosphinic acid methyl ester, (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,2,4-trimethylpentylphosphine oxide, 3,3-trimethyl-pentylphosphine oxide, and the like. Specifically, IRGACURE 819 (manufactured by BASF) as TPO (manufactured by Lamberti) and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide as 2,4,6-trimethylbenzoyl-diphenyl- And the like.

트리아진계 광중합개시제로서는 2,4,6-트리클로로-s-트리아진, 2-페닐-4,6-비스(트리클로로메틸)-s-트리아진, 2-(p-메톡시페닐)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(p-톨릴)-4,6-비스(트리클로로메틸)-s-트리아진, 2-피페로닐-4,6-비스(트리클로로메틸)-s-트리아진, 2,4-비스(트리클로로메틸)-6-스티릴-s-트리아진, 2-(나프토-1-일)-4,6-비스(트리클로로메틸)-s-트리아진, 2-(4-메톡시-나프토-1-일)-4,6-비스(트리클로로메틸)-s-트리아진, 2,4-트리클로로메틸-(피페로닐)-6-트리아진, 2,4-트리클로로메틸(4'-메톡시스티릴)-6-트리아진 등이 예시된다. As the triazine photopolymerization initiator, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s- triazine, 2- (p- methoxyphenyl) (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho- (Trichloromethyl) -s-triazine, 2,4-trichloromethyl- (2-methoxy-naphthol- Piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine and the like.

광중합개시제의 함유량은 클리어 잉크 조성물 중 5.0 질량% 이상인 것이 바람직하고, 더욱이 6.0 질량% 이상인 것이 바람직하다. 또한, 광중합개시제의 함유량은 클리어 잉크 조성물 중 15.0 질량% 이하인 것이 바람직하고, 더욱이 12.0 질량% 이하인 것이 바람직하다. 광중합개시제의 함유량이 5.0 질량% 미만인 경우, 클리어 잉크 조성물은 UV-LED 경화성이 저하되기 쉬울 가능성이 있다. 또한, 이 범위로 함으로써 경화 도막에 황변을 발생시키기 어렵다. 한편, 광중합개시제의 함유량이 15.0 질량%를 초과하면, 클리어 잉크 조성물은 추가로 광중합개시제를 배합하는 것에 따른 경화성의 효과가 향상되지 않아, 과잉 첨가가 되기 쉽다. The content of the photopolymerization initiator is preferably 5.0% by mass or more, more preferably 6.0% by mass or more in the clear ink composition. The content of the photopolymerization initiator in the clear ink composition is preferably 15.0 mass% or less, more preferably 12.0 mass% or less. When the content of the photopolymerization initiator is less than 5.0% by mass, the clear ink composition may be liable to lower the UV-LED curability. In addition, by setting this range, it is difficult to cause yellowing in the cured coating film. On the other hand, when the content of the photopolymerization initiator is more than 15.0 mass%, the clear ink composition does not improve the effect of the curing property by further blending the photopolymerization initiator and tends to be excessively added.

또한, 본 실시형태의 클리어 잉크 조성물은 아실포스핀계 광중합개시제를 5.0~15.0 질량% 배합하는 것이 바람직하고, 성능이 저하되지 않는 범위에서 다른 광중합개시제가 병용되어도 된다. 상기 광중합개시제로부터 1종 이상 또는 2종 이상을 사용할 수 있고, 또한 다른 광중합개시제로서 티옥산톤계 광중합개시제, α-히드록시케톤계 광중합개시제 등을 병용하는 것도 가능하다. The clear ink composition of the present embodiment is preferably blended with 5.0 to 15.0 mass% of an acylphosphine-based photopolymerization initiator, and other photopolymerization initiators may be used in combination within a range not deteriorating the performance. The photopolymerization initiator may be used alone or in combination of two or more. As the other photopolymerization initiator, a thioxanthone photopolymerization initiator, an? -Hydroxyketone photopolymerization initiator, or the like may be used in combination.

＜평균 입경 1~200 ㎚의 무기 필러＞ <An inorganic filler having an average particle diameter of 1 to 200 nm>

본 발명에 있어서 사용하는 평균 입경 1~200 ㎚, 바람직하게는 평균 입경 1~100 ㎚의 무기 필러로서는 체질안료가 바람직하고, 또한 실리카, 산화알루미늄, 탄산칼슘을 사용하는 것이 바람직하며, 더욱이 바람직하게는 실리카와 산화알루미늄이다. 또한, 이들 무기 필러를 1종 사용해도 되고, 2종 이상을 병용하는 것도 가능하다. As the inorganic filler for use in the present invention having an average particle size of 1 to 200 nm, preferably an average particle size of 1 to 100 nm, an extender pigment is preferable, and silica, aluminum oxide and calcium carbonate are preferably used, Is silica and aluminum oxide. These inorganic fillers may be used alone or in combination of two or more.

그리고 이들 안료를 필요에 따라 분쇄하여 그 평균 입경을 1~200 ㎚, 바람직하게는 1~100 ㎚로 한다. 또한, 여기서 말하는 평균 입경은 아래의 방법으로 측정하여 얻은 값이다. 평균 입경은 닛키소사 제조 Microtrac UPA-150을 사용해서 측정하였다. These pigments are pulverized as necessary to give an average particle diameter of 1 to 200 nm, preferably 1 to 100 nm. The average particle diameter is a value measured by the following method. The average particle diameter was measured using Microtrac UPA-150 manufactured by Nikkiso Co., Ltd.

평균 입경 1~200 ㎚의 무기 필러는 본 발명의 클리어 잉크 조성물 중 0.05~5.0 질량%, 바람직하게는 0.05~3.0 질량%가 되도록 배합된다. 배합량이 0.05 질량% 미만이면 열에 대한 안정성을 향상시킬 수 없어 보존 안정성이 떨어지게 되어 마이크로겔이 발생하기 쉬워진다. 배합량이 5.0 질량%를 초과하는 경우에는 자중 여과 시험결과 및 그의 촉진 시험결과가 불량하다. 　 The inorganic filler having an average particle diameter of 1 to 200 nm is compounded in an amount of 0.05 to 5.0% by mass, preferably 0.05 to 3.0% by mass in the clear ink composition of the present invention. If the blending amount is less than 0.05% by mass, the stability against heat can not be improved and the storage stability is lowered, and microgels are likely to be generated. When the blending amount exceeds 5.0% by mass, the result of the self weight filtration test and the result of the accelerated test thereof are inferior.

또한 평균 입경을 1 ㎚ 미만으로 하더라도 열에 대한 안정성의 추가적인 향상을 기대할 수 없고, 또한 그러한 매우 미세한 입경의 무기 필러를 제조하는 것이 곤란하다. Further, even if the average particle diameter is less than 1 nm, further improvement in stability against heat can not be expected, and it is also difficult to produce such an inorganic filler having a very fine particle size.

또한 평균 입경이 200 ㎚를 초과하는 경우에는 잉크 조성물 중에 균일하게 분산시키는 것이 곤란해지는 동시에, 열에 대한 안정성을 향상시킬 수 없어 보존 안정성이 떨어지게 되어 마이크로겔이 발생하기 쉬워진다. 또한, 자중 여과 시험의 촉진 시험결과가 불량하다. On the other hand, when the average particle diameter exceeds 200 nm, it is difficult to uniformly disperse the ink composition in the ink composition, and the stability against heat can not be improved, resulting in poor storage stability and microgels. Also, the result of the acceleration test of the self weight filtration test is poor.

또한, 첨가하는 무기 필러의 종류 및 그의 배합량으로서는, 본 발명의 잉크 조성물이 클리어 잉크인 것을 감안하여 그의 가시광 투과율을 30% 이상, 바람직하게는 50% 이상, 더욱 바람직하게는 70% 이상, 가장 바람직하게는 90% 이상이 되도록 한다. In view of the fact that the ink composition of the present invention is a clear ink, the kind of the inorganic filler to be added and the blending amount thereof are preferably not less than 30%, preferably not less than 50%, more preferably not less than 70% To be more than 90%.

(안료 분산제) (Pigment dispersant)

또한, 본 발명의 광경화형 잉크젯 인쇄용 클리어 잉크 조성물은 필요에 따라 안료 분산제를 함유하고 있어도 된다. In addition, the clear ink composition for photocurable inkjet printing of the present invention may contain a pigment dispersant if necessary.

안료 분산제는 안료의 분산성, 본 발명의 광경화형 잉크젯 인쇄용 잉크 조성물의 보존 안정성을 향상시키기 위해 사용하는 것으로, 종래부터 사용되고 있는 것을 특별히 제한 없이 사용할 수 있는데, 그중에서도 고분자 분산제를 사용하는 것이 바람직하다. 이러한 안료 분산제로서는, 카르보디이미드계 분산제, 폴리에스테르아민계 분산제, 지방산 아민계 분산제, 변성 폴리아크릴레이트계 분산제, 변성 폴리우레탄계 분산제, 다쇄형 고분자 비이온계 분산제, 고분자 이온 활성제 등을 들 수 있다. 이들 안료 분산제는 단독으로 또는 2종 이상을 혼합해서 사용할 수 있다.The pigment dispersant is used to improve the dispersibility of the pigment and the storage stability of the ink composition for photocurable inkjet printing of the present invention. Any conventionally used pigment may be used without particular limitation, and a polymer dispersant is preferably used. Examples of such pigment dispersants include carbodiimide dispersants, polyester amine dispersants, fatty acid amine dispersants, modified polyacrylate dispersants, modified polyurethane dispersants, multi-chain type polymeric nonionic dispersants, and polymeric ion activators . These pigment dispersants may be used alone or in combination of two or more.

상기 안료 분산제는 사용하는 전체 안료의 양을 100 질량부로 했을 때, 1~200 질량부 함유하는 것이 바람직하다. 안료 분산제의 함유량이 1 질량부 미만에서는, 안료 분산성, 본 발명의 잉크 조성물의 보존 안정성이 저하되는 경우가 있다. 한편, 200 질량부를 초과하여 함유시키는 것도 가능하나 효과에 차이가 없는 경우도 있다. 안료 분산제 함유량의 보다 바람직한 하한은 5 질량부, 보다 바람직한 상한은 60 질량부이다.The pigment dispersant is preferably contained in an amount of 1 to 200 parts by mass based on 100 parts by mass of the total pigment to be used. When the content of the pigment dispersant is less than 1 part by mass, the pigment dispersibility and the storage stability of the ink composition of the present invention may be deteriorated. On the other hand, it may be contained in an amount exceeding 200 parts by mass, but there may be no difference in effect. A more preferable lower limit of the content of the pigment dispersant is 5 parts by mass, and a more preferable upper limit is 60 parts by mass.

(케톤 수지) (Ketone resin)

본 발명의 광경화형 잉크젯 인쇄용 잉크 조성물에는 점착성이 생기는 것을 방지하기 위해 케톤 수지를 함유시키는 것도 가능하다. The ink composition for photocurable inkjet printing of the present invention may contain a ketone resin in order to prevent stickiness.

상기 케톤 수지로서는, 전술한 광중합성 화합물에 용해되는 것이라면 특별히 한정되는 것은 아니며, 공지의 케톤 수지를 사용할 수 있다. The ketone resin is not particularly limited as long as it is soluble in the above-mentioned photopolymerizable compound, and a known ketone resin can be used.

케톤 수지로서는 수산기를 갖는 케톤 수지가 바람직하고, 구체적으로는 예를 들면 (1) 아세토페논 등의 방향족계 케톤 화합물, 시클로헥사논이나 트리메틸시클로헥사논 등의 지환족계 케톤 화합물 등의 케톤기 함유 화합물과, 포름알데히드 등의 알데히드 화합물을 반응시켜서 얻어진 케톤 수지를 수소첨가하여 얻어지는 수산기를 함유하는 케톤 수지, (2) 이소시아네이트 화합물과 반응 가능한 치환기를 갖는 케톤 수지에 이소포론디이소시아네이트 등의 폴리이소시아네이트 화합물을 반응시켜서 얻어지는 수산기를 함유하는 우레탄 변성 케톤 수지 등을 들 수 있다. 이들은 각각 단독으로 사용해도 되고, 또한 2종류 이상 조합해서 사용해도 된다. The ketone resin is preferably a ketone resin having a hydroxyl group. Specific examples thereof include (1) ketone group-containing compounds such as aromatic ketone compounds such as acetophenone and alicyclic ketone compounds such as cyclohexanone and trimethylcyclohexanone And an aldehyde compound such as formaldehyde; (2) a ketone resin having a substituent capable of reacting with an isocyanate compound, and a polyisocyanate compound such as isophorone diisocyanate And a hydroxyl group-containing urethane-modified ketone resin obtained by reacting. These may be used alone or in combination of two or more.

그리고, 이들 케톤 수지는 시판되고 있으며, 구체적으로는 예를 들면 에보닉사 제조의 SK, PZZ-1201 등이 있다. These ketone resins are commercially available. Specific examples thereof include SK and PZZ-1201 manufactured by Evoniks.

상기 케톤 수지를 함유시킬 때는 그 함유량을 광경화형 잉크젯 인쇄용 잉크 조성물 중 5.0~15.0 질량%로 하는 것이, 점착성이 생기는 것을 방지하기 위해서는 바람직하다. When the ketone resin is contained, the content of the ketone resin in the ink composition for photo-curable inkjet printing is preferably 5.0 to 15.0 mass% in order to prevent stickiness from occurring.

본 발명의 클리어 잉크 조성물은 종래 주지의 방법으로 조제할 수 있다. 일례를 들면, 클리어 잉크 조성물은 예를 들면 상기한 각각의 성분 및 후술되는 임의 성분을 모두 혼합하고 교반함으로써 조제할 수 있다. 얻어지는 클리어 잉크 조성물의 25℃에 있어서의 점도는 1.0 mPa·s 이상으로 조정된다. 또한, 클리어 잉크 조성물의 25℃에 있어서의 점도는 10.0 mPa·s 이하이고, 바람직하게는 5.0 mPa·s 이하로 조정된다. 이러한 클리어 잉크 조성물은 잉크젯 기록장치에 의해 인쇄할 때의 토출 안정성이 우수하다. 특히, 이러한 클리어 잉크 조성물은 에너지 절약화, 고속화, 고정세화를 위해 저점도 잉크 대응으로서 설계된 잉크젯 기록장치의 헤드로부터의 상온에 있어서의 토출 안정성이 우수하다. The clear ink composition of the present invention can be prepared by a conventionally known method. For example, the clear ink composition can be prepared, for example, by mixing and stirring the above-mentioned respective components and any of the following optional components. The viscosity of the obtained clear ink composition at 25 캜 is adjusted to 1.0 mPa s or more. The viscosity of the clear ink composition at 25 캜 is 10.0 mPa s or less, preferably 5.0 mPa 쨌 s or less. Such a clear ink composition has excellent ejection stability when printed by an inkjet recording apparatus. In particular, such a clear ink composition is excellent in discharge stability at room temperature from the head of an inkjet recording apparatus designed for low viscosity ink for energy saving, high speed, and high definition.

또한, 본 실시형태의 클리어 잉크 조성물은 종래 주지의 방법으로 인자, 경화 가능하다. 일례를 들면, 클리어 잉크 조성물은 기재 또는 기재에 인자된 인쇄물(이하, 간단히 기재 등이라고도 함)에 토출된 후, 기재 등에 착탄(着彈)된 클리어 잉크 조성물의 도막을 UV-LED로 노광하여 경화시키는 방법에 의해 인자, 경화 가능하다. The clear ink composition of the present embodiment can be printed and cured by a conventionally known method. For example, the clear ink composition can be obtained by exposing the clear ink composition onto a substrate or a printed matter printed on the substrate (hereinafter simply referred to as a substrate or the like) and then exposing the coating film of the clear ink composition, And can be printed and cured by the method of making.

기재로서는 UV-LED 경화형 잉크젯 인쇄용 클리어 잉크 조성물에 종래부터 사용되고 있는 것이 특별히 제한 없이 사용된다. 구체적으로는, 종이, 플라스틱 필름, 캡슐, 금속박, 유리 등이 예시된다. 그중에서도 바닥재로서 사용되는 염화비닐, 폴리카보네이트 등이 바람직하다. As the substrate, those conventionally used in a clear ink composition for UV-LED curable inkjet printing are used without any particular limitation. Specific examples thereof include paper, a plastic film, a capsule, a metal foil and glass. Of these, vinyl chloride, polycarbonate and the like which are used as a bottom material are preferable.

본 실시형태의 클리어 잉크 조성물은 예를 들면 잉크젯 기록장치(잉크젯 프린터)의 저점도 대응의 프린터 헤드에 공급되어 프린트 헤드로부터 기재에 토출된다. 토출된 클리어 잉크 조성물은 막 두께가 예를 들면 1~60 ㎛가 되도록 기재에 착탄된다. 착탄된 클리어 잉크 조성물은 UV-LED가 조사됨으로써 적당히 경화된다. 또한, 본 실시형태의 클리어 잉크 조성물을 인자하는 잉크젯 기록장치로서는, 종래 주지의 잉크젯 기록장치가 이용된다. 이때, 연속식 타입(continuous type)의 잉크젯 기록장치가 사용되는 경우에는, 클리어 잉크 조성물은 추가로 도전성 부여제가 첨가되어 전도도가 적절히 조절되는 것이 바람직하다. The clear ink composition of the present embodiment is supplied to, for example, a printer head corresponding to a low viscosity of an inkjet recording apparatus (inkjet printer), and is ejected from the printhead to the substrate. The discharged clear ink composition is deposited on the substrate so that the film thickness is, for example, 1 to 60 mu m. The deposited clear ink composition is suitably cured by irradiation with UV-LED. As the ink jet recording apparatus for printing the clear ink composition of the present embodiment, a conventionally known ink jet recording apparatus is used. At this time, when a continuous type ink jet recording apparatus is used, it is preferable that the clear ink composition is further added with a conductivity imparting agent so that the conductivity is appropriately controlled.

＜클리어 잉크 조성물의 임의 성분＞&Lt; Optional components of clear ink composition &gt;

다음으로, 본 실시형태의 클리어 잉크 조성물이 적합하게 포함하는 임의 성분에 대해서 설명한다. 본 실시형태의 클리어 잉크 조성물은 상기한 성분 이외에도, 각종 기능을 발현시키기 위해 임의 성분이 적당히 배합되어도 된다. 예를 들면 클리어 잉크 조성물은 계면활성제, 용제, 염료, 기타 착색안료 등의 안료, 증감제, 안료 분산제 및 각종 첨가제가 포함되어도 된다. Next, arbitrary components suitably included in the clear ink composition of the present embodiment will be described. In the clear ink composition of the present embodiment, in addition to the above-described components, optional components may be appropriately blended to express various functions. For example, the clear ink composition may contain a pigment such as a surfactant, a solvent, a dye and other colored pigments, a sensitizer, a pigment dispersant, and various additives.

(계면활성제) (Surfactants)

계면활성제는 클리어 잉크 조성물이 사용되는 잉크젯 기록장치의 헤드에 따라, 클리어 잉크 조성물의 토출 안정성 등을 향상시키기 위해 적당히 배합되어도 된다. 계면활성제로서는 종래부터 광경화형 잉크젯 인쇄용 잉크 조성물에 적합하게 사용되고 있는 실리콘계 계면활성제 등이 예시된다. 구체적으로는, 실리콘계 계면활성제로서 폴리에테르 변성 실리콘 오일, 폴리에스테르 변성 폴리디메틸실록산, 폴리에스테르 변성 메틸알킬폴리실록산 등이 예시된다. 이들 계면활성제는 병용되어도 된다. The surfactant may be appropriately compounded in order to improve the discharge stability and the like of the clear ink composition according to the head of the ink jet recording apparatus in which the clear ink composition is used. As the surfactant, a silicone surfactant conventionally used suitably for an ink composition for photocurable inkjet printing is exemplified. Specifically, examples of the silicone surfactant include a polyether-modified silicone oil, a polyester-modified polydimethylsiloxane, and a polyester-modified methylalkylpolysiloxane. These surfactants may be used in combination.

계면활성제의 함유량은 클리어 잉크 조성물 중 0.005 질량% 이상인 것이 바람직하다. 또한, 계면활성제의 함유량은 클리어 잉크 조성물 중 1.0 질량% 이하인 것이 바람직하다. 계면활성제의 함유량이 0.005 질량% 미만인 경우, 클리어 잉크 조성물은 표면장력이 커져 토출 안정성이 저하되기 쉽다. 한편, 계면활성제의 함유량이 1.0 질량%를 초과하는 경우, 클리어 잉크 조성물은 기포를 포함하기 쉬워 토출 안정성이 저하되기 쉽다. The content of the surfactant is preferably 0.005 mass% or more in the clear ink composition. The content of the surfactant is preferably 1.0% by mass or less in the clear ink composition. When the content of the surfactant is less than 0.005% by mass, the clear ink composition tends to have a large surface tension, and thus the discharge stability tends to deteriorate. On the other hand, when the content of the surfactant is more than 1.0% by mass, the clear ink composition tends to contain bubbles, which tends to lower the discharge stability.

(용제)(solvent)

용제는 클리어 잉크 조성물에 적당히 배합되어도 된다. 용제로서는 에스테르계 유기 용제, 에테르계 유기 용제, 에테르에스테르계 유기 용제, 케톤계 유기 용제, 방향족 탄화수소 용제, 함질소계 유기 용제 등이 예시된다. 또한, 용제로서는 상압(1.013×102 kPa)에 있어서의 비점이 150~220℃인 것이 예시된다. The solvent may be appropriately blended in the clear ink composition. Examples of the solvent include an ester organic solvent, an ether organic solvent, an ether ester organic solvent, a ketone organic solvent, an aromatic hydrocarbon solvent, a nitrogen-containing organic solvent and the like. As the solvent, the boiling point at normal pressure (1.013 x 10 2 kPa) is 150 to 220 ° C.

유기 용제는 클리어 잉크 조성물의 경화성, 환경문제 등의 관점에서 최대한 사용되지 않는 것이 바람직하다. 이 때문에 유기 용제의 함유량은 클리어 잉크 조성물 중 5 질량% 이하인 것이 바람직하고, 2 질량% 이하인 것이 보다 바람직하며, 사용되지 않는 것이 더욱 바람직하다. It is preferable that the organic solvent is not maximally used from the viewpoints of the curability of the clear ink composition, environmental problems, and the like. Therefore, the content of the organic solvent in the clear ink composition is preferably 5% by mass or less, more preferably 2% by mass or less, and further preferably not used.

(기타 안료)(Other pigment)

각색의 클리어 잉크 조성물을 얻기 위해 평균 입경 1~200 ㎚의 무기 필러 이외의 안료를 적당히 배합해도 된다. 이러한 안료로서는 통상의 광경화형 잉크젯 인쇄용 잉크 조성물에 종래부터 사용되고 있는 것으로, 구체적으로는 클리어 잉크 조성물에 양호하게 분산되고, 내후성이 우수한 유기 안료 또는 무기 필러가 바람직하다. 구체적으로는, 상기 유기 안료로서는 염료 레이키 안료, 아조계, 벤즈이미다졸론계, 프탈로시아닌계, 퀴나크리돈계, 안트라퀴논계, 디옥사진계, 인디고계, 티오인디고계, 페릴렌계, 페리논계, 디케토피롤로피롤계, 이소인돌리논계, 니트로계, 니트론계, 플라반트론계, 퀴노프탈론계, 피란트론계, 인단트론계의 안료 등을 들 수 있다. 이들 안료는 병용되어도 된다. A pigment other than an inorganic filler having an average particle diameter of 1 to 200 nm may be appropriately blended to obtain a clear ink composition of each color. Such a pigment is conventionally used in conventional ink compositions for photocurable ink-jet printing, specifically, an organic pigment or an inorganic filler that is well dispersed in a clear ink composition and has excellent weather resistance is preferable. Specific examples of the organic pigments include organic pigments such as dye lake colors, azo pigments, benzimidazolone pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, perylene pigments, perinone pigments, A pyrrolone-based pigment, an isoindolinone-based pigment, a nitro-based pigment, a nitrone pigment, a flavanthrone pigment, a quinophthalone pigment, a pyranthrone pigment and an indanthrone pigment. These pigments may be used in combination.

다만, 이들 안료를 배합할 때는 평균 입경 1~200 ㎚의 무기 필러를 배합하는 것에 따른 효과를 방해하지 않도록 하는 것이 필요하다. However, when these pigments are blended, it is necessary not to interfere with the effect of blending the inorganic filler having an average particle diameter of 1 to 200 nm.

(증감제) (Sensitizer)

본 발명의 광경화형 잉크젯 인쇄용 클리어 잉크 조성물에는, 추가로, 발광 다이오드(LED)를 광원으로 한 자외선에 대한 경화성을 촉진시키기 위해, 400 ㎚ 이상의 주로 자외선의 파장역에서 광흡수 특성을 가져, 그 범위의 파장의 빛에 의해 경화반응의 증감기능이 발현되는 광증감제(화합물)를 병용 사용할 수 있다. The clear ink composition for photocurable inkjet printing of the present invention further has a light absorbing property at a wavelength range of ultraviolet light of 400 nm or more in order to promote curability against ultraviolet rays using a light emitting diode (LED) as a light source, (Compound) in which the function of increasing and decreasing the curing reaction is expressed by the light of the wavelength of the light-sensitive agent can be used in combination.

또한, 상기 「400 ㎚ 이상의 파장의 빛에 의해 증감기능이 발현된다」는 것은, 400 ㎚ 이상의 파장역에서 광흡수 특성을 갖는 것을 말한다. 이러한 증감제를 사용함으로써, 본 발명의 광경화형 잉크젯 인쇄용 클리어 잉크 조성물의 LED 경화성을 촉진시킬 수 있다. Further, the expression &quot; a sensitizing function is expressed by light having a wavelength of 400 nm or more &quot; means that the light absorbing property is exhibited in a wavelength region of 400 nm or more. By using such a sensitizer, the LED curing property of the clear ink composition for photocurable inkjet printing of the present invention can be promoted.

상기 광증감제로서는, 안트라센계 증감제, 티옥산톤계 증감제 등이며, 바람직하게는 티옥산톤계 증감제이다. 이들은 단독 도는 2종 이상을 병용해서 사용할 수 있다. As the photosensitizer, an anthracene-based sensitizer, a thioxanthone-based sensitizer, and the like, preferably a thioxanthone sensitizer. These may be used alone or in combination of two or more.

구체적으로는, 9,10-디부톡시안트라센, 9,10-디에톡시안트라센, 9,10-디프로폭시안트라센, 9,10-비스(2-에틸헥실옥시)안트라센 등의 안트라센계 증감제, 2,4-디에틸티옥산톤, 2-이소프로필티옥산톤, 4-이소프로필티옥산톤 등의 티옥산톤계 증감제를 들 수 있다. 시판품의 대표예로서는, 안트라센계 증감제로서는 DBA, DEA(가와사키 화성공업사 제조), 티옥산톤계 증감제로서는 DETX, ITX(LAMBSON사 제조) 등을 예시할 수 있다. 단, 변색 방지를 위해 티옥산톤계 증감제는 사용하지 않는 편이 좋다. Specific examples thereof include anthracene type sensitizers such as 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene and 9,10-bis (2-ethylhexyloxy) And thioxanthone sensitizers such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 4-isopropylthioxanthone. Representative examples of commercially available products include DBA and DEA (manufactured by Kawasaki Chemical Industry Co., Ltd.) as anthracene-based sensitizers, and DETX and ITX (manufactured by LAMBSON) as thioxanthone sensitizers. However, it is better not to use thioxanthone sensitizer to prevent discoloration.

(각종 첨가제) (Various additives)

각종 첨가제로서는 열경화성 수지, 광안정화제, 표면처리제, 점도저하제, 산화방지제, 노화방지제, 가교촉진제, 중합금지제, 가소제, 방부제, pH 조정제, 소포제, 보습제 등이 적당히 배합되어도 된다. As the various additives, a thermosetting resin, a photostabilizer, a surface treatment agent, a viscosity reducing agent, an antioxidant, an antioxidant, a crosslinking accelerator, a polymerization inhibitor, a plasticizer, a preservative, a pH adjuster, a defoaming agent and a humectant may be appropriately mixed.

이상과 같이, 본 실시형태의 클리어 잉크 조성물은 40~90 질량%의 단관능 모노머, 15~50 질량%의 다관능 모노머 및 5~15 질량%의 아실포스핀계 광중합개시제를 포함한다. 이러한 클리어 잉크 조성물은 UV-LED 경화성이 우수하다. As described above, the clear ink composition of the present embodiment contains 40 to 90 mass% monofunctional monomer, 15 to 50 mass% polyfunctional monomer, and 5 to 15 mass% acylphosphine-based photopolymerization initiator. This clear ink composition is excellent in UV-LED curing property.

또한, 얻어지는 경화 도막은 기재에 대한 밀착성, 내찰성이 우수하다. Further, the resulting cured coating film is excellent in adhesion and scratch resistance to a substrate.

실시예Example

아래에 실시예를 들어 본 발명을 더욱 상세하게 설명하는데, 본 발명은 이들 실시예에만 한정되는 것은 아니다. 또한 특별히 언급이 없는 한, 「%」는 「질량%」를 의미하고, 「부」는 「질량부」를 의미한다. Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" means "mass%" and "part" means "mass part".

아래의 실시예, 비교예에서 사용한 재료는 다음과 같다. The materials used in the following examples and comparative examples are as follows.

＜안료 분산제＞ <Pigment dispersant>

아지스퍼(등록상표) PB821(아지노모토 파인테크노 주식회사 제조) Agisper (registered trademark) PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.)

＜광중합성 화합물＞ &Lt; Photopolymerizable compound &gt;

벤질아크릴레이트(오사카 유기 화학공업사 제조) Benzyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

비닐카프로락탐 1,6-헥산디올디아크릴레이트 Vinyl caprolactam 1,6-hexanediol diacrylate

＜광중합개시제＞ <Photopolymerization initiator>

TPO：2,4,6-trimethylbenzoyl diphenyl phosphine oxide(LAMBERTI사 제조)TPO: 2,4,6-trimethylbenzoyl diphenyl phosphine oxide (manufactured by Lamberti)

＜첨가제＞ <Additives>

BYK-315(실리콘 첨가제, BYK Chemie사 제조)BYK-315 (silicone additive, manufactured by BYK Chemie)

UV-5＝말레산디옥틸(크로마켐사 제조) UV-5 = dioctyl maleate (manufactured by Chroma Chemical)

UV-22＝퀴논류 중합금지제(크로마켐사 제조) UV-22 = quinone polymerization inhibitor (manufactured by Chroma Chemical Co.)

＜무기 산화물＞ <Inorganic Oxide>

실리카(입경 20 ㎚, NANOCRYL C 140, Evonik사 제조, 1,6-헥산디올디아크릴레이트 중에 분산시킨 것, 고형분 50%)Silica (particle diameter 20 nm, NANOCRYL C 140, manufactured by Evonik, dispersed in 1,6-hexanediol diacrylate, solid content 50%),

산화알루미늄(입경 80 ㎚, AEROXIDE Alu-C, 일본 에어로실, 자사 분산, 고형분 10%)Aluminum oxide (particle diameter 80 nm, AEROXIDE Alu-C, Japan Aerosil, self dispersion, solid content 10%)

＜산화알루미늄 분산물의 조제＞ <Preparation of Aluminum Oxide Dispersion>

AEROXIDE Alu-C를 10 질량부, 분산제로서 PB-821을 1 질량부, 벤질아크릴레이트를 89 질량부를 레디밀(비드 직경：0.2 ㎚, 충전율 50%)로 60분간 분쇄하여 점도 4.9 cps, 입도분포 80 ㎚의 고형분 10%의 산화알루미늄 분산물을 얻었다. 10 parts by mass of AEROXIDE Alu-C, 1 part by mass of PB-821 as a dispersing agent, and 89 parts by mass of benzyl acrylate were pulverized for 60 minutes with Redi mill (bead diameter: 0.2 nm, packing rate 50%) to obtain a viscosity of 4.9 cps, A 10% solid aluminum oxide dispersion of 80 nm was obtained.

＜실시예 1~8 및 비교예 1~3＞ &Lt; Examples 1 to 8 and Comparative Examples 1 to 3 &gt;

〔광경화형 잉크젯 인쇄용 클리어 잉크 조성물의 조제〕[Preparation of clear ink composition for photocurable inkjet printing]

표 1의 배합 조성(질량%)이 되도록 각 성분을 배합하고 교반 혼합하여, 실시예 1~8, 비교예 1~3의 광경화형 잉크젯 인쇄용 클리어 잉크 조성물을 얻었다.Each component was compounded so as to have a composition (mass%) shown in Table 1 and stirred and mixed to obtain a clear ink composition for photocurable inkjet printing of Examples 1 to 8 and Comparative Examples 1 to 3.

〔광경화형 잉크젯 인쇄용 클리어 잉크 조성물의 점도 측정〕 [Viscosity measurement of clear ink composition for photocurable inkjet printing]

실시예 1~8 및 비교예 1~3에서 얻어진 각 광경화형 잉크젯 인쇄용 클리어 잉크 조성물에 대해서, E형 점도계(상품명：RE100L형 점도계, 도키산교사 제조)를 사용하여, 온도 25℃, 로터 회전속도 50 rpm의 조건으로 점도를 측정하였다. Each of the clear ink compositions for photo-curable inkjet printing obtained in Examples 1 to 8 and Comparative Examples 1 to 3 was evaluated for viscosity at 25 占 폚 by using an E-type viscometer (trade name: RE100L type viscometer, The viscosity was measured under the condition of 50 rpm.

실시예 1~8, 비교예 1~3의 광경화형 잉크젯 인쇄용 클리어 잉크 조성물의 점도는 약 7 mPa·s였다. The viscosity of the clear ink composition for photocurable inkjet printing of Examples 1 to 8 and Comparative Examples 1 to 3 was about 7 mPa · s.

＜가시광 투과율＞ <Visible light transmittance>

가시광 투과율은 자외·가시 분광광도계(상품명：UV-Vis Recording Spectrophotometer, 시마즈 제작소사 제조)에 의해 측정하였다.Visible light transmittance was measured by an ultraviolet / visible spectrophotometer (trade name: UV-Vis Recording Spectrophotometer, manufactured by Shimadzu Corporation).

＜자중 여과 시험＞ <Self weight filtration test>

실시예 1~8, 비교예 1~3의 광경화형 잉크젯 인쇄용 클리어 잉크 조성물의 제조 직후(초기) 및 60℃ 1개월 보존 후, 각 광경화형 잉크젯 인쇄용 클리어 잉크 조성물 40 g을 SPC 필터 홀더(Φ25 ㎜, 시바타 과학사 제조)에 2600 메시를 사용하여 통과시켜서 통과도를 측정하였다. (Initial) and 60 占 폚 for one month after the preparation of the clear ink composition for photocurable inkjet printing of Examples 1 to 8 and Comparative Examples 1 to 3, 40 g of each clear ink composition for photo-curable inkjet printing was applied to an SPC filter holder , Manufactured by Shibata Scientific Co., Ltd.) using 2600 mesh to measure the degree of penetration.

Figure pct00001
Figure pct00001

　본 발명에 따른 예인 실시예 1~8에 의하면, 가시광 투과율이 높은 클리어 잉크임에도 불구하고, 60℃에서 1개월 촉진(보존) 후에 있어서도 제조 직후의 초기 상태와 비교하여 거의 변함없는 저장 안정성을 구비하고 있다. 이에 대해, 무기 필러의 함유량이 부족한 비교예 1, 과잉으로 첨가한 비교예 2, 평균 입경이 큰 무기 필러를 첨가한 비교예 3에 의하면, 60℃ 1개월 후에 있어서 변질되어 있었다. 무기 필러를 과잉으로 첨가하거나 무기 필러가 지나치게 큰 경우에는, 제조 직후에 있어서 이미 저장 안정성이 떨어져 있었다.According to Examples 1 to 8 according to the present invention, despite the clear ink having a high visible light transmittance, even after one month of promotion (storage) at 60 DEG C, the ink has substantially the same storage stability as compared with the initial state immediately after production have. On the other hand, according to Comparative Example 1 in which the content of the inorganic filler was insufficient, Comparative Example 2 in which excess amount of inorganic filler was added, and Comparative Example 3 in which inorganic filler having a large average particle size was added, When the inorganic filler was excessively added or the inorganic filler was too large, the storage stability was already poor immediately after the production.

Claims (6)

광중합성 화합물, 광중합개시제 및 평균 입경 1~200 ㎚의 무기 필러를 조성물 중 0.05~5.0 질량% 함유하고, 가시광 투과율이 30% 이상인 광경화형 잉크젯 인쇄용 클리어 잉크 조성물. A photopolymerizable compound, a photopolymerization initiator, and 0.05 to 5.0% by mass of an inorganic filler having an average particle diameter of 1 to 200 nm in the composition, and a visible light transmittance of 30% or more. 제1항에 있어서,
무기 필러가 실리카 및/또는 산화알루미늄인 광경화형 잉크젯 인쇄용 클리어 잉크 조성물. The method according to claim 1,
Wherein the inorganic filler is silica and / or aluminum oxide. 제1항 또는 제2항에 있어서,
아미노기 및/또는 산기를 갖는 안료 분산제를 함유하는 광경화형 잉크젯 인쇄용 클리어 잉크 조성물. 3. The method according to claim 1 or 2,
A clear ink composition for photocurable inkjet printing comprising a pigment dispersant having an amino group and / or an acid group. 제1항 내지 제3항 중 어느 한 항에 있어서,
광중합성 화합물로서, 광경화형 잉크젯 인쇄용 클리어 잉크 조성물 중에 아미드기를 갖는 단관능 모노머와 벤질아크릴레이트의 합계량으로 50~75 질량% 함유하는 광경화형 잉크젯 인쇄용 클리어 잉크 조성물. 4. The method according to any one of claims 1 to 3,
A clear ink composition for photocurable inkjet printing comprising a photopolymerizable compound in a total amount of monofunctional monomer having amide group and benzyl acrylate in a clear ink composition for photocurable inkjet printing. 제1항 내지 제4항 중 어느 한 항에 있어서,
아미드기를 갖는 단관능 모노머가 N-비닐카프로락탐 및/또는 아크릴로일모르폴린인 광경화형 잉크젯 인쇄용 클리어 잉크 조성물. 5. The method according to any one of claims 1 to 4,
Wherein the monofunctional monomer having an amide group is N-vinylcaprolactam and / or acryloylmorpholine. 제1항 내지 제5항 중 어느 한 항에 있어서,
25℃의 점도가 10 mPa·s 이하인 광경화형 잉크젯 인쇄용 클리어 잉크 조성물. 6. The method according to any one of claims 1 to 5,
Wherein the viscosity at 25 占 폚 is 10 mPa 占 퐏 or less.
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